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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
NASA NTRS1999

Combustion of Interacting Droplet Arrays in a Microgravity Environment

Investigations into droplet interactions date back to Rex et al. Recently, Annamalai and Ryan and Annamalai published extensive reviews of droplet array and cloud combustion studies. The authors studied the change in the burning rate constant, k, (relative to that of the single droplet) that results from interactions. Under certain conditions, there exists a separation distance where the droplet lifetime reaches a minimum, or average burning rate constant is a maximum . Additionally, since inter-droplet separation distance, L, increases relative to the droplet size, D, as the burning proceeds, the burning rate is not constant throughout the burn, but changes continuously with time. Only Law and co-workers and Mikami et al. studied interactions under conditions where buoyant forces were negligible. Comparing their results with existing theory, Law and co-workers found that theory over predicted the persistency and intensity of droplet interactions. The droplet interactions also depended on the initial array configuration as well as the instantaneous array configuration. They also concluded that droplet heating was retarded due to interactions and that the burning process did not follow the "D-squared" law. Mikami et al. studied the combustion of a two-droplet array of heptane burning in air at one atm pressure in microgravity. They showed that the instantaneous burning rate constant increases throughout the droplet lifetime, even for a single droplet. Also, the burn time of the array reached a minimum at a critical inter-droplet spacing. In this article, we examine droplet interactions in normal and microgravity environments. The microgravity experiments were in the NASA GRC 2.2 and 5.2 second drop towers, and the JAMIC (Japan Microgravity Center) 10 second drop tower. Special emphasis is directed to combustion under conditions that yield finite extinction diameters, and to determine how droplet interactions affect the extinction process.

Dietrich, D. L.↗
NASA NTRS1982

Modeling of polymer photodegradation for solar cell modules

It was shown that many of the experimental observations in the photooxidation of hydrocarbon polymers can be accounted for with a computer simulation using an elementary mechanistic model with corresponding rate constants for each reaction. For outdoor applications, however, such as in photovoltaics, the variation of temperature must have important effects on the useful lifetimes of such materials. The data bank necessary to replace the isothermal rate constant values with Arrhenius activation parameters: A (the pre-exponential factor) and E (the activation energy) was searched. The best collection of data assembled to data is summarized. Note, however, that the problem is now considerably enlarged since from a theoretical point of view, with 51 of the input variables replaced with 102 parameters. The sensitivity of the overall scheme is such that even after many computer simulations, a successful photooxidation simulation with the expanded variable set was not completed. Many of the species in the complex process undergo a number of competitive pathways, the relative importance of each being often sensitive to small changes in the calculated rate constant values.

Somersall, A. C.↗
DOE OSTI2026

Restricted Partition Function Semiclassical Transition State Theory (RPF-SCTST): Applications to Reactions Involving Hydrogen Cyanide, Hydrogen Peroxide, and Formaldehyde Oxide

We demonstrate the efficiency of the numerical calculation of thermal semiclassical transition state theory (SCTST) rates across several representative chemical reactions using the restricted partition function (RPF)─viz a function that depends only on the imaginary action associated with a reaction. Here, we treat the potential energy surfaces (PESs) through fourth order expansions around the saddle point and integrate the Hamiltonian up to second order in employing vibrational perturbation theory. We apply this formalism to uni- and bimolecular reactions with different─though relatively high─barrier heights to uncover the influence of the barrier properties, minimal energies, and separability of the rotational motion on rate constants and tunneling corrections. Although all modes are coupled within the RPF, we found in our numerical examples that the rotational component in the absence of significant rotational distortions can be separated from the vibrational contributions. Moreover, a classical treatment of the rotational contribution is adequate over the temperature range from approximately 100 to 1000 K. We also found that the choice of DFT basis set can lead to variations in rate constants of up to an order of magnitude. Lastly, different schemes for counting eligible energy levels result in rate constants that differ by no more than a factor of 2, with the remaining discrepancies attributed to the treatment of near-convergent levels in perturbation theory.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1994

Effect of vibrationally excited oxygen on ozone production in the stratosphere

Photolysis of vibrationally excited oxygen produced by ultraviolet photolysis of ozone in the upper stratosphere is incorporated into the Lawrence Livermore National Laboratory two-dimensional zonally averaged chemical-radiative-transport model of the troposphere and stratosphere. The importance of this potential contributor of odd oxygen to the concentration of ozone is evaluated based on recent information on vibrational distributions of excited oxygen and on preliminary studies of energy transfer from the excited oxygen. When energy transfer rate constants similar to those of Toumi et al. (1991) are assumed, increases in model ozone concentrations of up to 4.0% in the upper stratosphere are found, and the model ozone concentrations are found to agree slightly better with measurements, including recent data from the Upper Atmosphere Research Satellite. However, the ozone increase is only 0.3% when the larger energy transfer rate constants indicated by recent experimental work are applied to the model. An ozone increase of 1% at 50 km requires energy transfer rate constants one-twentieth those of the preliminary observations. As a result, vibrationally excited oxygen processes probably do not contribute enough ozone to be significant in models of the upper stratosphere.

Patten, K. O., Jr.↗
DOE OSTI2024

Homomolecular Triplet–Triplet Annihilation in Metalloporphyrin Photosensitizers

Metalloporphyrins are ubiquitous in their applications as triplet photosensitizers, particularly for promoting sensitized photochemical upconversion processes. In this study, bimolecular excited state triplet–triplet quenching kinetics, termed homomolecular triplet–triplet annihilation (HTTA), exhibited by the traditional triplet photosensitizers–zinc(II) tetraphenylporphyrin (ZnTPP), palladium(II) octaethylporphyrin (PdOEP), platinum(II) octaethylporphyrin (PtOEP), and platinum(II) tetraphenyltetrabenzoporphyrin (PtTPBP)–were revealed using conventional transient absorption spectroscopy. Nickel(II) tetraphenylporphyrin was used as a control sample as it is known to be rapidly quenched intramolecularly through ligand-field state deactivation and, therefore, cannot result in triplet–triplet annihilation (TTA). The single wavelength transients associated with the metalloporphyrin triplet excited state decay–measured as a function of incident laser pulse energy in toluene–were well modeled using parallel first- and second-order kinetics, consistent with HTTA being operable. The combined transient kinetic data enabled the determination of the first-order rate constants (k T ) for excited triplet decay in ZnTPP (4.0 × 10 3 s –1 ), PdOEP (3.6 × 10 3 s –1 ), PtOEP (1.2 × 10 4 s –1 ), and PtTPBP (2.1 × 10 4 s –1 ) as well as the second-order rate constant (k TT ) for HTTA in ZnTPP (5.5 × 10 9 M –1 s –1 ), PdOEP (1.1 × 10 10 M –1 s –1 ), PtOEP (7.1 × 10 9 M –1 s –1 ), and PtTPBP (1.6 × 10 10 M –1 s –1 ). In most instances, triplet excited state extinction coefficients are either reported for the first time or have been revised using ultrafast transient absorption spectroscopy and singlet depletion: ZnTPP (78,000 M –1 cm –1 ) at 470 nm, PdOEP (67,000 M –1 cm –1 ) at 430 nm, PtOEP (51,000 M –1 cm –1 ) at 418 nm, and PtTPBP (100,000 M –1 cm –1 ) at 460 nm. Furthermore, the combined experimental results establish competitive time scales for homo- and heteromolecular TTA rate constants, implying the significance of considering HTTA processes in future research endeavors harnessing TTA photochemistry using common metalloporphyrin photosensitizers.

14 SOLAR ENERGY↗
DOE OSTI2021

Transport Modeling of Kinetically Limited Microscale Extraction Systems: Droplet and Supported Liquid Membrane Separations

Microfluidic droplet extraction devices can be used to efficiently measure solute phase transfer kinetics in liquid–liquid extraction systems. In this work, a droplet extraction apparatus was constructed using off-the-shelf and custom 3D printed parts for less than 110 USD. The interfacial kinetics of the transfer of Pu(IV) between an aqueous nitric acid phase and a 5 v/v% tridodecylamine (TDA) in toluene phase were characterized by determining the extent of Pu(IV) transfer between phases at different flow rates. Forward interfacial rate constants calculated from this data using an analytical model are 5.6 × 10 –3 mm s –1 under extraction (aqueous-to-organic solute transfer) conditions and 3.3 × 10 –3 mm s –1 under stripping (organic-to-aqueous solute transfer) conditions. The analytical model is valid when the rate of solute transfer across the interface between the two liquid phases has pseudo-first-order reversible reaction kinetics and is slow relative to the rate of solute transport to the interface. The change in the outlet concentration with residence time determined using the analytical model was compared with the results of a numerical model accounting for advection/diffusion to the interface in addition to kinetically limited interfacial solute transfer. These calculations revealed that for systems with forward interfacial rate constants greater than approximately 10 –2 mm s –1 , the analytical model must be supplemented with a numerical transport model accounting for an additional advection/diffusion mass transfer resistance. This threshold corresponds to a Damköhler number of one. The measured interfacial kinetic rate constants for Pu(IV)/TDA were used in a supported liquid membrane (SLM) numerical model, which showed that the Pu(IV) phase transfer kinetics are fast enough for use in a practical separation.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS1992

Theoretical study of thermodynamic properties and reaction rates of importance in the high-speed research program

One of the primary goals of NASA's high-speed research program is to determine the feasibility of designing an environmentally safe commercial supersonic transport airplane. The largest environmental concern is focused on the amount of ozone destroying nitrogen oxides (NO(x)) that would be injected into the lower stratosphere during the cruise portion of the flight. The limitations placed on NO(x) emission require more than an order of magnitude reduction over current engine designs. To develop strategies to meet this goal requires first gaining a fundamental understanding of the combustion chemistry. To accurately model the combustor requires a computational fluid dynamics approach that includes both turbulence and chemistry. Since many of the important chemical processes in this regime involve highly reactive radicals, an experimental determination of the required thermodynamic data and rate constants is often very difficult. Unlike experimental approaches, theoretical methods are as applicable to highly reactive species as stable ones. Also our approximation of treating the dynamics classically becomes more accurate with increasing temperature. In this article we review recent progress in generating thermodynamic properties and rate constants that are required to understand NO(x) formation in the combustion process. We also describe our one-dimensional modeling efforts to validate an NH3 combustion reaction mechanism. We have been working in collaboration with researchers at LeRC, to ensure that our theoretical work is focused on the most important thermodynamic quantities and rate constants required in the chemical data base.

Langhoff, Stephen↗
NASA NTRS1997

Rate Coefficients for Reactions of Ethynyl Radical (C2H) With HCN and CH3CN: Implications for the Formation of Comples Nitriles on Titan

Rate coefficients for the reactions of C2H + HCN yields products and C2H + CH3CN yields products have been measured over the temperature range 262-360 K. These experiments represent an ongoing effort to accurately measure reaction rate coefficients of the ethynyl radical, C2H, relevant to planetary atmospheres such as those of Jupiter and Saturn and its satellite Titan. Laser photolysis of C2H2 is used to produce C2H, and transient infrared laser absorption is employed to measure the decay of C2H to obtain the subsequent reaction rates in a transverse flow cell. Rate constants for the reaction C2H + HCN yields products are found to increase significantly with increasing temperature and are measured to be (3.9-6.2) x 10(exp 13) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 297-360 K. The rate constants for the reaction C2H + CH3CN yields products are also found to increase substantially with increasing temperature and are measured to be (1.0-2.1) x 10(exp -12) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 262-360 K. For the reaction C2H + HCN yields products, ab initio calculations of transition state structures are used to infer that the major products form via an addition/elimination pathway. The measured rate constants for the reaction of C2H + HCN yields products are significantly smaller than values currently employed in photochemical models of Titan, which will affect the HC3N distribution.

Hoobler, Ray J.↗
NASA NTRS1986

Pressure and temperature dependences of the reaction of OH with nitric acid

Rate constants for the reaction of OH with HNO3 have been measured by using a laser flash photolysis resonance absorption technique at 298 and 248 K in the presence of 10-730 Torr of He, N2, and SF6. A dependence on total pressure was observed with rate constant values increasing at 298 K from 1.11 x 10 to the -13th cu cm/molecule/s at 10 Torr to 1.45 x 10 to the -13th cu cm/molecule/s at 730 Torr, and at 248 K from 1.87 x 10 to the -13th cu cm/molecule/s at 10 Torr to 3.07 x 10 to the -13th cu cm/molecule/s at 730 Torr with helium as the diluent gas. Falloff behavior occurred at lower pressures with SF6 or N2 as the diluent gas. Extrapolated zero pressure rate constants were determined and correspond to an Arrhenius activation energy of E/R = -710 K.

Stachnik, R. A.↗
NASA NTRS2003

Ultra-High-Temperature Ceramics Evaluated for Aeropropulsion Use

Ultra-high-temperature ceramics (UHTC) are a group of materials consisting of zirconium diboride (ZrB2) or hafnium diboride (HfB2) plus silicon carbide (SiC), and in some instances, carbon (C). They offer a combination of properties that make them candidates for airframe leading edges on sharp-bodied reentry vehicles. These UHTCs perform well in the environment for such applications (i.e., air at low pressures). The purpose of this study at the NASA Glenn Research Center was to examine three of these materials under conditions more representative of a propulsion environment: that is, higher oxygen partial pressure and total pressure. Relatively long, multiple-exposure cycles were emphasized. We completed an in-house study of ZrB2 plus 20 vol% SiC (abbreviated as ZS), ZrB2 plus 14 vol% SiC and 30 vol% C (ZSC), and SCS-9a SiC fiber-reinforced ZrB2 plus 20 vol% SiC (ZSS). HfB2-based compositions were not included in the study because of their high cost. The capability of UHTC for propulsion applications must be compared with that of mature, available, and commercially used ceramics such as silicon nitride (e.g., AS-800) to put things in proper perspective. In terms of mechanical properties, UHTCs fall short in terms of strength and fracture toughness. At about 1300 C, the creep resistance of ZS appears to be superior to the creep resistance reported for AS-800. However, the stress rupture life for Si3N4 under stress and temperature conditions similar to those used in this study is measured in hundreds of hours. Because of oxidation, ZS could not achieve such lives. In terms of oxidation resistance, acceptable amounts of material recession in 1 hour to thousands of hours, depending on the specific propulsion application, are on the order of 100 to 300 mm. This converts to an acceptable range of parabolic recession rate constants kp" of approximately less than or equal to 10(exp -1) to 10(exp -2) square millimeters per hour for a 1-hr application. For a 100-hr application, an acceptable range of kp" would be less than or equal to those values divided by 100. For the more oxidation resistant ZS material, measured parabolic recession rate constants were 4.7 x 10(exp -3) millimeters per hour at 1327 C, 7.8 x 10(exp -2) square millimeters per hour at 1627 C, and 1.3 millimeters per hour at 1927 C. Thus, recession rate constants for ZS are acceptable at 1327 C for a 1-hr application, but here silicon nitride is a superior material. At 1627 C, ZS oxidation is marginal for a 1-hr application, but dimensional growth would be an issue. In a 100-hr application, ZS cannot be considered at any temperature. Our cursory examination of thermal shock, both from a theoretical and experimental viewpoint, indicated that the ZS and ZSC UHTCs are inferior to AS-800 silicon nitride. On the basis of this limited study, UHTCs are not ready to be considered as aeropropulsion materials for any applications longer than a few minutes. Current materials suffer from aggressive oxidation and moisture attack (Quynhgiao Nguyen, NASA Glenn, and Raymond C. Robinson, QSS Group, Inc., Cleveland, OH, 2002, private communication), and they are susceptible to thermal shock. For long-term propulsion applications, major improvements in environmental durability are needed. Work is in progress to improve the oxidation resistance of UHTC materials.

Levine, Stanley R.↗
DOE OSTI2025

A theoretical kinetic study of ĊH 3 + ṄH 2 : From electronic structure to NH 3 /CH 4 combustion modelling implications

Carbon–nitrogen interaction reactions play an important role in governing the reactivity of ammonia blended fuels. However, there remains uncertainties regarding their detailed reaction pathways and rate constants, hampering the development of high-fidelity chemical kinetic models. In this study, the kinetics of ĊH 3 + ṄH 2 , a key C–N interaction reaction in ammonia/methane blend combustion have been investigated. The potential energy surface has been explored using the high-level ANL0F method, yielding highly accurate stationary point energies that agree with ATcT values within 0.1 kcal mol –1 . Variable reaction coordinate transition state theory is used to treat the barrierless association and decomposition reaction channels, based on directly sampled radical-radical interaction energies at the CASPT2-F12(2e,2o)/cc-pVTZ-F12 level of theory. The minimum transitional mode numbers of states obtained are then coupled with the RRKM/master equation to calculate temperature- and pressure-dependent rate constants. Our a priori calculations capture available experimental measurements from the literature very well. The calculated rate constants have been incorporated into an NH 3 /CH 4 chemical kinetic model currently under development at the University of Galway. The effect of the updated kinetic data for ĊH 3 + ṄH 2 on model predicted NH 3 /CH 4 fuel reactivity is elucidated.

ab initio↗
NASA NTRS1985

QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis

Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of catonic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR'P(O)X, where R and R' are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrogen hydrolysis rate constant.

Johnson, H.↗
NASA NTRS1985

QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis

Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of cationic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR-primeP(O)X, where R and R-prime are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrolysis rate constant.

Johnson, H.↗
DOE OSTI2024

Probabilistic and maximum entropy modeling of chemical reaction systems: Characteristics and comparisons to mass action kinetic models

We demonstrate and characterize a first-principles approach to modeling the mass action dynamics of metabolism. Starting from a basic definition of entropy expressed as a multinomial probability density using Boltzmann probabilities with standard chemical potentials, we derive and compare the free energy dissipation and the entropy production rates. We express the relation between entropy production and the chemical master equation for modeling metabolism, which unifies chemical kinetics and chemical thermodynamics. Because prediction uncertainty with respect to parameter variability is frequently a concern with mass action models utilizing rate constants, we compare and contrast the maximum entropy model, which has its own set of rate parameters, to a population of standard mass action models in which the rate constants are randomly chosen. We show that a maximum entropy model is characterized by a high probability of free energy dissipation rate and likewise entropy production rate, relative to other models. We then characterize the variability of the maximum entropy model predictions with respect to uncertainties in parameters (standard free energies of formation) and with respect to ionic strengths typically found in a cell.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1973

Gas phase recombination of hydrogen and deuterium atoms

Rate constants for the reaction H + H + M - H2 + M, with M = H2, He, and Ar were measured over the temperature range 77 to 298 K. Hydrogen atoms were produced by thermal dissociation and absolute atom concentrations were measured through use of self-balancing, isothermal catalytic probe detector. The specific rate constants were 8.1 + or - 0.4 x 10 to the minus 33rd power, 7.0 + or - 0.4 x 10 to the minus 33rd power, and 9.2 + or - 0.6 x at 298 K for M = H2, He, and Ar respectively; these values rising to 18.5 + or - 2.2 x 10 to the minus 33rd power, 12.0 + or - 1.5 x 10 to the minus 33rd power, and 27.4 + or - 4.6 x 10 to the minus 33rd power cm to the 6th power/molecules sq/sec at 77 K. for the equivalent deuterium atom process with D2 as the third body, the rate constants are 6.1 + or - 0.3 x 10 to the minus 33rd power cm to the 6th power/molecules sq/sec at 298 K and 15.1 + or - 1.0 x 10 to the minus 33rd power cm to the 6th power/molecules sq/sec at 77 K. These values are compared with previous experimental measurements and with recent theoretical calculations.

Trainor, D. W.↗
NASA NTRS1984

Kinetics of the reaction HO2 + NO2 + M yields HO2NO2 + M

The flash photolysis/ultraviolet absorption technique was used to measure the rate constants for the reaction HO2 + NO2 + M yields HO2NO2 + M over the pressure range 50-700 torr and temperature range 229-362 K using He, O2, and N2 as diluent gases. The data were fit to the expression derived by Troe (1979) and co-workers for describing the pressure and temperature dependence of reactions in the falloff region. By combining these data with recent measurements of the rate constant for HO2NO2 thermal decomposition values of 73.8 + or - 2 eu for the standard entropy and -12.6 + or - kcal/mol for the standard enthalpy of formation of HO2NO2 were obtained. A significant enhancement in the rate constant was observed when water vapor was added to the system.

Sander, S. P.↗
NASA NTRS2001

Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid surfaces. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants; (i.e., amphiphiles with a hydrophobic moiety consisting of an extended chain of (aliphatic) methylene -CH2- groups attached to a large polar group to give aqueous solubility) are capable of reducing the contact angles on surfaces which are not very hydrophobic, but do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm, polyethylene or self assembled monolayers. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3) and an extended ethoxylate (-(OCH2CH2)a-) polar group in the form of a chain with four or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (termed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread. We propose that the trisiloxane surfactants superspread because their structure allows them to strongly lower the high hydrophobic solid/aqueous tension when they adsorb to the solid surface. When the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross-sectional area of the disk is larger than that of the extended ethoxylate chain, the disks can form a space-filling mat on the surface which removes a significant amount of the surface water. In this presentation, we report the results of measurements of the molecular packing and rates of kinetic exchange of the trisiloxane surfactants at the air/water interface in order to confirm our picture of trisiloxane packing, and provide additional insight into the superspreading process. We used the pendant bubble technique as a Langmuir trough to measure the trisiloxane equation of state which relates the tension to the surface concentration. From these measurements we obtain accurate values for the maximum packing density. We find that trisiloxanes with 4 and 8 ethoxylate groups have the same maximum packing concentration, indicating that the maximum packing is controlled by the cross section of the head group. For trisiloxanes with larger than eight ethoxylates, the maximum packing increases with ethoxylate number, indicating that the disposition of the ethoxylate chain (i.e., its effective size) is controlling. This supports our picture of superspreading: The superspreading ability of trisiloxanes decreases considerably for trisiloxanes with larger than eight ethoxylates; the packing measurements indicate that for the higher ethoxylate number trisiloxanes, the compact nonpolar head groups are pushed apart by the ethoxylate chain. They leave spaces of surface water on adsorption and do not lower the solid tension as much as their lower chain analogues. Finally the report measurements of the dynamic tension reduction accompanying the adsorption of trisiloxanes onto an initially clean interface using the pendant bubble technique, and we obtain from these relaxations, the equation of state and a mass transfer model, the rate constants for kinetic exchange. We find that the rate constants for desorption of trisiloxanes are generally much slower than for analogous aliphatic polyethoxylate surfactants with identical ethoxylate chain lengths. When an aqueous drop of a superspreader solution is placed on a hydrophobic surface and begins to spread, the lower desorption rates allows the tension at the drop center to remain reduced relative to the tension of the expanding periphery, thus strengthening Marangoni forces which can assist the spreading. Marangoni forces can be especially significant in the case of superspreaders because their maximum equilibrium reduction in tension is several dynes/cm lower than for aliphatic surfactants.

Kumar, Nitin↗
DOE OSTI2022

Predicting third-body collision efficiencies for water and other polyatomic baths

Low-pressure-limit microcanonical (collisional activation) and thermal rate constants are predicted using a combination of automated ab initio potential energy surface construction, classical trajectories, transition state theory, and a detailed energy- and angular-momentum-resolved collision kernel. Several systems are considered, including CH 4 (+M) and HO 2 (+M), with an emphasis on systems where experimental information is available for comparison. The a priori approach involves no adjustable parameters, and we show that the predicted thermal rate constants are in excellent agreement with experiments, with average deviations of less than 25%. Notably, the a priori approach is shown to perform equally well for atomic, diatomic, and polyatomic baths, including M = H 2 O, CO 2 , and “fuel” baths like M = CH 4 and NH 3 . Additionally, the utility of microcanonical rate constants for interpreting trends and inferring mechanistic details in the thermal kinetics is demonstrated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗